Carbon Dioxide → Ammonia

HRID 2387687Notes

Reaction equation

HRID 2387687 reaction equation
C([Li])CCC.Br[C:7]1[CH:8]=[C:9]([CH:38]=[CH:39][CH:40]=1)[CH2:10][O:11][CH:12]1[CH2:17][CH2:16][N:15]([C:18]([CH3:37])([CH3:36])[CH2:19][CH2:20][C:21]([C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[C:22]#[N:23])[CH2:14][CH2:13]1.C(=O)=O>O1CCCC1>[NH3:15].[CH2:10]([O:11][CH:12]1[CH2:13][CH2:14][N:15]([C:18]([CH3:37])([CH3:36])[CH2:19][CH2:20][C:21]([C:24]2[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=2)([C:30]2[CH:31]=[CH:32][CH:33]=[CH:34][CH:35]=2)[C:22]#[N:23])[CH2:16][CH2:17]1)[C:9]1[CH:8]=[CH:7][CH:40]=[CH:39][CH:38]=1

Participants

6

Reactant 3

HCID 280Carbon DioxideHCID 59423969HCID 59423969, compoundHCID 178418339Butyllithium

Product 2

HCID 222AmmoniaHCID 59423905HCID 59423905, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

n-Butyl lithium (2.5M in hexanes, 0.23 mL, 0.56 mmol) was added dropwise to a solution of the product of example 87 (200 mg, 0.38 mmol) in tetrahydrofuran (8 mL), cooled to −78° C., and the mixture was stirred for 30 minutes. Carbon dioxide was then passed through the solution, with stirring at −78° C., for 3.5 hours before the mixture was allowed to warm to room temperature. The reaction mixture was concentrated in vacuo and the residue was partitioned between ethyl acetate (30 mL) and water (20 mL). The organic layer was separated, washed with water, dried over magnesium sulfate and concentrated in vacuo. Purification of the residue by column chromatography on silica gel, eluting with dichloromethane:methanol:0.88 ammonia, 100:0:0 to 98:2:0.2, afforded the title compound as a by-product, as an off white solid in 68% yield, 116 mg.

Workup

  1. stirringwith stirring at −78° C., for 3.5 hours before the mixture
  2. temperatureto warm to room temperature
  3. concentrationThe reaction mixture was concentrated in vacuo
  4. customthe residue was partitioned between ethyl acetate (30 mL) and water (20 mL)
  5. customThe organic layer was separated
  6. washwashed with water
  7. dry with materialdried over magnesium sulfate
  8. concentrationconcentrated in vacuo
  9. customPurification of the residue by column chromatography on silica gel
  10. washeluting with dichloromethane

Sources & evidence

ORD record
ord-0c9e070efc3e40099d0a9e8bcdb113fd
Source dataset
uspto-grants-2012_09
Patent number
US08268881B2

Reaction notes

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